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This paper describes the preparation and characterization of MgO and ZnO-based catalysts, pure and mixed in different proportions, supported on γ-Al2O3. Their catalytic performance was studied in the transesterification of soybean oil and castor oil with methanol and butanol, attempting to produce biodiesel. XRD (X-ray diffraction), SEM–EDS (scanning electron microscopy–energy dispersive X-ray spectroscopy), CO2-adsorption and N2-adsorption allowed characterizing the prepared catalysts. The characterization results were in all cases consistent with mesoporous solids with high specific surface area. All the catalysts exhibited good results, especially in the transesterification of castor oil using butanol. For this reaction, the reuse was tested, maintaining high FABE (fatty acid butyl esters) yields after four cycles. This good performance can be attributed to the basic properties of the Mg species, and simultaneously, to the amphoteric properties of ZnO, which allow both triglycerides and free fatty acids to be converted into esters. Using these catalysts, it is possible to obtain second-generation biodiesel, employing castor oil, a raw material that does not compete with the food industry. In addition, butanol can be produced from renewable biomass.

This work presents the synthesis, characterization, and application of zirconium oxide (ZrO2)-based catalysts, modified with macro (silica nanospheres, NSP-SiO2) and mesopore templates (Pluronic 123), impregnated with tungstophosphoric acid (TPA), in the catalytic pyrolysis of tomato agro-industrial residues. The NSP-SiO2 (SXX) and P123 (PYY) amount mainly influences the ZrO2SXXPYY-specific surface area (SBET) and average pore diameter (Dp). 31P MAS NMR and FT-IR characterization results show that TPA (H3PW12O40) was partially transformed into [P2W21O71]6− and [PW11O39]7− during the synthesis steps. The acidic properties of ZrO2SXXPYY samples containing 25 and 50 wt% of TPA (ZrO2SXXPYYT25 and ZrO2SXXPYYT50, respectively) are dependent on both the TPA content and the support nature. Bio-oil composition and product selectivity were strongly influenced by the textural and acid-based properties of the catalysts. Notably, non-catalytic pyrolysis favored pathways leading to C2 compounds, with a high content of acetic acid and hydroxyacetone. In contrast, the use of catalysts promoted the formation of higher molecular weight oxygenated compounds (C5–C6), specifically furans, aldehydes, and ketones.

Palladium-modified Co-ZnAland Cu-ZnAl materials were used and found active for the catalytic oxidation of propene and propane. According to the results obtained by XRD, TPR and XPS, the zinc aluminate-supported phases are oxide phases, Co3O4, CuO and PdOx for Co-ZnAl, Cu-ZnAl and Pd-ZnAl catalysts, respectively. These reducible oxide species present good catalytic activity for the oxidation reactions. The addition of palladium to Co-ZnAl or Cu-ZnAl samples promoted the reducibility of the system and, consequently, produced a synergic effect which enhanced the activity for the propene oxidation. The PdCo-ZnAl sample was the most active and exhibited highly dispersed PdOx particles and surface structural defects. In addition, it exhibited good catalytic stability. The H2 pre-treated PdCu-ZnAl, PdCo-ZnAl and Pd-ZnAl samples showed higher activity than the original oxide catalysts, evidencing the important role of the oxidation state of the species, mainly of the palladium species, on the catalytic activity for the propene combustion. The synergic effect between metal transition oxides and PdOx could not be observed for the propane oxidation.

Catalytic pyrolysis has been used to upgrading the quality of pyrolytic liquids. Herein, we report a comprehensive study on the catalytic pyrolysis of waste tires using Ni/SiO 2 as catalysts. The analyses were carried out by combining thermogravimetry (TGA), TGA interfaced to a Fourier transform infrared spectrometer (TGA–FTIR), and pyrolysis coupled to gas chromatography/mass spectrometer (Py–GC/MS) techniques. During waste tire decomposition, the main functional groups detected in the FTIR were alkenes, aromatics, and heteroatoms-containing groups such as nitrogen, sulfur, and oxygen. Meanwhile, by Py–GC/MS were identified mainly D,L-limonene, isoprene, benzene, toluene, xylenes (BTX), and p-cymene. The Py–GC/MS experiments at three different temperatures (350, 400, and 450 °C) suggested an effect of the catalyst on product distribution. The Ni catalyst promoted cyclization reactions and subsequently aromatization, leading to an improved vapors composition. The use of iso-conversional kinetic models along with master plots allows proposing a multiple-step reaction mechanism, which was well described by the Avrami–Erofeev, Random Scission, and truncated Sestak–Berggren models. The values of activation energies show differences for the catalyzed and uncatalyzed pyrolysis (111.0 kJ mol −1 and 168.4 kJ mol −1 ), validating the effectivity of Ni/SiO 2 . Finally, the thermal Biot (> 1) and Py I and Py II numbers (10 –3  < Py I  < 10 –1 and 10 –2  < Py II  < 10 –3 ) confirms that the process is being occurred between the kinetic and the convection-limited regimes. Graphic Abstract

The use of tomato plant residues (i.e., stems, leaves, etc.) as a substrate for catalytic pyrolysis of biomass was investigated. A comprehensive study was conducted to investigate the impact of catalysts on the performance of different pyrolysis fractions (i.e., gas, biosolid, waxes, and bioliquid) as well as the distribution of products within the bioliquid. The catalysts employed in this study were derived from two distinct types of zirconia. The first type was synthesized by a conventional sol-gel method, while the second type was prepared with a modified method aimed at improving the presence of mesopores. This modification involved the incorporation of Pluronic 123. These materials were designated ZrO2 and ZrO2P25, respectively. Both types of zirconia were used as supports for tungstophosphoric acid (H3PW12O40, TPA), a heteropolyacid with a Keggin structure, in the preparation of catalysts with strong acid sites. The results demonstrated that the bioliquid yield of the non-catalytic fast pyrolysis of tomato plant waste was approximately 23% and that the obtained bioliquid contained a wide variety of molecules, which were detected and quantified by GC-MS. In the presence of the catalysts, both the bioliquid yield and the distribution of bioliquid products were substantially modified. Furthermore, the possible sugar degradation pathways leading to the formation of the molecules present in the pyrolytic bioliquids were thoroughly examined. The results obtained from this study indicate that the physicochemical characteristics of the catalysts, specifically their pore size and acidity, have a significant impact on the selectivity of the catalytic processes towards valuable molecules, including anhydro-sugars and furanic derivatives such as furfural and furfuryl alcohol.

Molecular modelling studies were carried out at the DFT level of the adsorption of propane and propene on Ag surfaces as a model of the interaction of light hydrocarbons with Ag/ZrO2 catalysts for catalytic combustion reactions. It was found that the most stable mode of adsorption of propene through its π system on Ag atom has energies consistent with chemisorption and generates an elongation of the C1=C2 bond, which would explain the increase in the activity of the catalysts as a function of its metallic charge. The results obtained from the DFT calculations explain the different types of interactions between propene and propane with the metallic surface. The propene is chemisorbed on the Ag surface, distorting its bonds and generating its activation. This would imply that a higher metallic charge in the catalyst would increase the number of active sites in which this activation occurs, generating a higher activity. In addition, with the addition of O, the binding energy between the propene and the metal surface increased. On the other hand, the presence of a metallic surface is not enough for the activation of the propane molecule. This would explain why, by increasing the amount of metal in the catalyst, the activity for the combustion of propane is practically not affected.

ZrO2 nH2O (hydrogel) impregnated with transition metals (Cu, Co, and Ni) was studied in this work as a precursor for the synthesis of CuO/ZrO2 (CuZ), CoOx/ZrO2 (CoZ), and NiO/ZrO2 (NiZ) catalysts, employed in the naphthalene oxidation reaction. Fresh and catalytically used materials were characterized by different physicochemical techniques, to compare the bulk and surface behavior, with particular attention to the effect of the supported metal species’ properties on the catalytic activity. Techniques such as X-ray diffraction (XRD), temperature programmed reduction (TPR), differential scanning calorimetry (DSC), Brunauer–Emmett–Teller (BET) surface area analyzer, diffuse reflectance spectroscopy (DRS UV–vis), and Raman spectroscopy, allow for establishing structural and textural aspects of the support, as well as the surface coordination and the accessibility of supported species. Results were in agreement with the CuZ > CoZ > NiZ sequence for the activity in naphthalene oxidation reaction. Electronic properties, ionic sizes, oxide phase deposition on the support surface, reducibility, metal–support interaction, and local site symmetry of metals seem to be decisive factors for the catalytic interaction with the gaseous phase.

This work presents the physicochemical characterization and activity of zirconia-supported silver catalysts for the oxidation of pollutants present in diesel engine exhaust (propane, propene, naphthalene and soot). A series of silver-supported catalysts AgxZ (x = 1, 5 and 10 wt.%, Z = zirconia) were prepared, which were studied by various characterization techniques. The results show that silver is mainly found under the form of small metal nanoparticles (<10 nm) dispersed over the support. The metallic phase coexists with the AgOx oxidic phases. Silver is introduced onto the zirconia, generating Ag–ZrO2 catalysts with high activity for the oxidation of propene and naphthalene. These catalysts also show some activity for soot combustion. Silver species can contribute with zirconia in the catalytic redox cycle, through a synergistic effect, providing sites that facilitate the migration and availability of oxygen, which is favored by the presence of structural defects. This is a novel application of the AgOx–Ag/ZrO2 system in the combustion reaction of propene and naphthalene. The results are highly promising, given that the T50 values found for both model molecules are quite low.

Zirconia-supported gold-promoted cobalt catalysts were synthesized and tested for the complete oxidation of propane and naphthalene. The catalysts were characterized by BET surface area, scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), powder X-ray diffraction (XRD), transmission electron microscopy (TEM), temperature-programmed reduction (TPR), and X-ray photoelectron spectroscopy (XPS). In both propane and naphthalene combustion reactions, the results obtained indicate that catalysts formulated with Co3O4 are more active than those containing only Au. Catalysts prepared using the deposit/precipitation (DP) method have better activity than those in which the traditional technique is used. Gold addition using the DP methods generates a promoting effect on the activity of cobalt-containing catalysts. The AuDpCoZt catalyst was found to be the most active for both propane and naphthalene combustion. The catalytic behavior of this sample is associated with a synergic effect between gold, cobalt, and the support, which is also evidenced by an increase in the reducibility of this catalytic system. The effect of the presence of NO in the feed was also analyzed for propane combustion.

Molecular modelling studies were carried out at the DFT level of the adsorption of propane and propene on Ag surfaces as a model of the interaction of light hydrocarbons with Ag/ZrO[sub.2] catalysts for catalytic combustion reactions. It was found that the most stable mode of adsorption of propene through its π system on Ag atom has energies consistent with chemisorption and generates an elongation of the C1=C2 bond, which would explain the increase in the activity of the catalysts as a function of its metallic charge. The results obtained from the DFT calculations explain the different types of interactions between propene and propane with the metallic surface. The propene is chemisorbed on the Ag surface, distorting its bonds and generating its activation. This would imply that a higher metallic charge in the catalyst would increase the number of active sites in which this activation occurs, generating a higher activity. In addition, with the addition of O, the binding energy between the propene and the metal surface increased. On the other hand, the presence of a metallic surface is not enough for the activation of the propane molecule. This would explain why, by increasing the amount of metal in the catalyst, the activity for the combustion of propane is practically not affected.